Production of valuable organic products



y 1934- M. PIER ET AL 1,959,175

PRODUCTION OF VALUABLE ORGANIC PRODUCTS I Filed May 25. 1928 r0 65/ 0/74 azsmz/arl Mower/mum 20m:

Patented ay '15,-

STATES PRODUCTION OF VALUABLE onoANIo raonoors l,05,l'i

Price Delaware Application May 25, 1928, Serial No. 280,642 I lln Germany May 28, 192? 9 Claims.

This invention relates to the production of valuable organic products, in particular liquid hydrocarbons, by the treatment of distillable solid carbonaceous substances, especially coal or substances of the nature of coal including peat,

5 wood, brown-coal and the "like at an elevated temperature.

We have found that in the production of valuable organic products by heat treatment of they said carbonaceous materials, if desired with application of pressure, and together with or in the absence of inert or hydrogenating gases, with or without an addition of solvents and with or without the employment of catalysts, namely in destructive hydrogenation or destructive distillation, it is very advantageous to first subject the said initial materials to a preliminary treatment which breaks up and loosens the aterial, in a manner disrupting the capillary skeleton of the initial material, thus rendering the material more suitable for the further treatment and in particular liberating the vaporous or liquid constituents contained therein or such as are capable of being liquefied at an elevated temperature, or at least rendering these readily accessible to 2 the further treatment. In this way the decomposition of the carbonaceous material in the further treatment is greatly facilitated and the yield of valuable liquid products is greatly increased.

The said preliminary treatment consists in a treatment under pressure usually without an addition of liquid organic solvents, at a temperature which is higher than that .employed in the ordinary briquetting processes, that is to, say usually above 100 C/but should be substantially below the coking point of the carbonaceous material. Thus the said treatment may be carried out at temperatures of between 200 and 450 but preferably between 300 and 400 C.

The preliminary treatment may consist for example in heating the initial materials i. e. the distillable solid carbonaceous substance referred to above in a closed apparatus inthe absence of 45 an added solvent so that they are exposed to the pressure of their own vapors.

The materials may also be subjected to mechanical pressing in a heated condition, the tem-. perature employed being, however, higher than in ordinary briquetting, or the pressure may be produced by admitting gases substantially free from hydrogen, such as nitrogen, carbon dioxid, water vapor and the like. The degree of pressure and the duration of thetreatment depends on the products to be treated and on the nature of the process in the further treatment; which, in turn, is modified to suit the products desired. Pressures of 50, 100, 200 or even 1000 atmospheres and more are employed.

The initial materials to be subjected to the preliminary treatment may be employed in the form of aqueous pastes which may be free-flowing or rather thick in consistency. Thelsaid initial material may also however be treated in the presence of or suspended in other non-solvents for the liquid products obtained, for example molten or liquid metals, such as lead, tin, bismuth, mercury and alloys of low melting point hereinafter referred to as metals liquid at the reaction temperature;

In certain circumstances it is advisable to add other substances, which may be solids, liquids or gases substantially free from hydrogen, during the preliminary treatment under pressure, since, by such means, the subsequent decomposition of the carbonaceous substances can be considerably increased and accelerated Particularly suitable for this purpose are substances with an alkaline reaction, such as oxides, hydroxides and carbonates of alkali or alkaline earth metals or sulfids containing strongly basic constituents, like the sulfids of the alkali metals and alkaline earth metals, but other substances'either inert or' exhibiting catalytic properties, may also be employed, such as iodine or other metalloids.

The initial materials which have undergone the said preliminary treatment are then subjected either partially orin their entirety to a heattreatment proper for the production of valuable products, in particular of liquid hydorcarbons, from carbonaceous materials as aforesaid. For example the liquid constituents may be separated from the solid constituents and the two'portions be treated separately.

In the preliminary treatment injurious sub-. stances, such as free iron, nickel, and the like capable under the specified condtions of giving'rise to secondary reactions such as the formation of coke and undesirable gases should preferably be excluded.

The nature of the present invention will be further explained with reference to the accompanying drawing diagrammatically showing a plant in which the process according to this invention may be carried out with advantage.

Referring to this drawing, in detail numeral 3 denotes a stirring vessel provided with a stirrer 3a. Into this vessel comminuted coal is introduced at -1, while an aqueous solution of sodium sulphide is supplied at 2. The coal is pasted up with the said solution of sodium sulphide and then, by tillable solid carbonaceous materials, which commeans of pump 4, conveyed into the preheating prises subjecting said materials to a preliminary coil 5, from whence it is passed into the high heat treatment at a. temperature above 100 (3., pressure vessel 6. In this high pressure vessel but below the coking point of said carbonaceous 5 the preliminary treatment, which breaks up and materials and under a pressure of at least 50 '80 loosens the material in a manner disrupting the atmospheres, while excluding added organic solcapillary skeletonthereof, takes place. The ma vents and gases containing a substantial amount terials issuing from tlie said high pressure vesof hydrogen to thereby disrupt the capillary skeleselare then led into the cooler 7 and from thence, ton of said materials and liquefy a, large portion 10 by way f pr ure release valv 8, int a centhereof, separating the resulting liquids from the 85 t'rif in Which th liq id parts res'eparated solids and separately destructively hydrogenatfrom the solid constituents. The solid constituin said separated liquid and solid products. ents areremoved at 10,- The liquid constituents 2. The process as defined in claim 1 whereinpass thr u h th p rforat d sid wall f the nthe preliminary heat treatment is effected in the 1 trifuge and a t n pu p d y m a s of pu p presence of a substance having an alkaline re- 90 11 into the preheating coil 14, whereupon they action pass in th h pressure vess l 15 in w h 3. The process as defined in claim 1 wherein h y are u j d to destructiv hy r i the preliminary heat treatment is carried out in y means of y e uppli d at 13 and likethe presence of a sulphide of a strongly basic wise preheated in the preheating coil 14. The metal products having undergone destructive hydro- 4 The prqcess as defined-in claim 1 wheregenation are cooled in cooler 16 and then passed in t prelhhinary t t t t i ff t d i into vessel 17 from which the liquid portions of t presence of t i the said products may be withdrawn at 19 while The process defined in claim 1 h i the uncondensed gases escape at the distillable carbonaceous material is .brown 100 The following example further illustrates the coal nature of this invention which however is no The process as defined in claim 1 whererestricted thereto- I l in the preliminary heat treatment is carried out Example, in the presence of a metal, liquid at the temperature employed in said'heat treatment and. 105

Brown-C0211 IS-mede Into a Paste Wlth Waiter selected from the class consisting of lead, tin,

and 5 to 10 per cent of sodium sulfid, and forced bismuth, mercury and alloys containing one f at 200 atmospheres and at about 360 Centigrade, said metals.

by means of a pump through high pressure 7. The process as defined in claim 1 wherein paratus the interior of which 15 constructed or a liquids produced in the preliminary heat 110 Steel contalmng a high percentage of chrommm treatment are separately subjected to destrucand nickel, the pressure being then released after five hydrogenation. cooling BY this means upto 50 Per cent of 8. The process as defined in claim 1 wherein H the coal substance is liquefied, practically withh solids obtained in t preliminary t t atout any production of mentare separately subjected to destructive hy- 115 The liquid constituents of the reaction product dmgenation. r are then separated from the solids, and the for- 9, The st t v hydrogenation of brownm are again p p through a high-Pressure coal, which comprises making brown coal into apparatus, in which they are treated, at 200 ata paste t water and subjecting t t mospheles and at atempera-ture o 4 to 4 liminary treatment in the presence of an alkali eentigrade W t yd in the presence of a metal sulfld at about 360 C. to a pressure of molybdenum-chromium catalyst; 200 atmospheres, thereupon separating the liq- The eflluent products from this treatment conuid products obtained and then subjecting these tain about 25 per cent of benzine, the'remainder to a treatment with hydrogen at a pressure of 50 consisting of hydrocarbon pro ducts boiling up to 200 at p and at a temperature of about 350 ti r d 440 to 450 C. in the presence of a molybdenum What we claim is:-- chromium catalyst. 1. A process for the production of valuable liq- S P ER- uid organic products, in particular liquid hydro- KARL W K ER- 55 carbons, by the destructive hydrogenation of dis- KURT WISSEL- 

